N-phenyl-pyrrol bisphosphane compounds and the metal complexes of the same

ABSTRACT

N-Phenylpyrrolebisphosphines of the formula I 
                         
metal complexes of these N-phenylpyrrolebisphosphines and their use in metal-catalyzed reactions.

The present invention relates to N-phenylpyrrolebisphosphines and theirmetal complexes, to their preparation and to their use in catalyticreactions.

Phosphorus compounds as ligands for metals in catalytic reactions havebeen known for some time. The type of ligand can be used to influenceactivity and selectivities (chemoselectivity, regioselectivity,diastereoselectivity, enantioselectivity, etc.) within a wide range.Bidentate ligands are often far superior to monodentate ligands.

For instance, U.S. Pat. Nos. 4,694,109 and 4,879,416 describebisphosphine ligands and their use in the hydroformylation of olefins atlow synthesis gas pressures. Especially in the hydroformylation ofpropene, ligands of this type allow high activities and high n/iselectivities to be achieved. WO 95/30680 discloses bidentate phosphineligands and their use in catalysis, in hydroformylation reactions amongothers. Ferrocene-bridged bisphosphines are described, for example, inthe patents U.S. Pat. Nos. 4,169,861, 4,201,714 and 4,193,943 as ligandsfor hydroformylations.

In asymmetric hydrogenations, chiral bisphosphines are used verysuccessfully in many cases. A known example is the ligand BINAP(2,2′-bis(diphenylphosphino)-1,1′-binaphthyl) which is even commerciallyobtainable. This ligand has also been used in many other metal-catalyzedreactions, for example in the Heck reaction.

The technical literature includes a variety of publications whichdescribe the use of ligands in conjunction with metals as catalysts. Agood review of the current state of the field of use for transitionmetal catalysts in organic synthesis can be found in Matthias Beller,Carsten Bolm (Ed.), “Transition Metals for Organic Synthesis”,Wiley-VCH, Weinheim, New York, Chichester, Brisbane, Singapore, Toronto,1998, Vol. 1&2. Examples of catalysts and their fields of use, commonindustrial scale processes, etc., can be found in B. Cornils, W. A.Herrmann (Ed.), “Applied Homogeneous Catalysis with OrganometallicCompounds”, VCH, Weinheim, New York, Basle, Cambridge, Tokyo, 1996, Vol.1&2.

Despite the wealth of existing systems, there are no “standardsolutions” for metal-catalyzed reactions. The conditions have to benewly optimized for each substrate and reaction. In addition, someligands are relatively difficult to synthesize, so that their use inindustrial processes is not viable.

There is therefore a need for further easily accessible ligand systemsfor metal-catalyzed reactions.

It has been found that N-phenylpyrrolebisphosphines of the generalstructure I

can be prepared in a simple manner and are suitable as ligands inmetal-catalyzed reactions.

The present invention therefore provides N-phenylpyrrolebisphosphines ofthe general formula I

where

R¹, R², R³, R⁴=aliphatic, cycloaliphatic or aromatic hydrocarbonradicals having from 1 to 25 carbon atoms, and R¹ and R² and/or R³ andR⁴ may be joined by one or more covalent bonds,

R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹=H, aliphatic, alicyclic,aliphatic-alicyclic, heterocyclic, aliphatic-heterocyclic, aromatic,aromatic-aromatic, aliphatic-aromatic hydrocarbon radicals having from 1to 50 carbon atoms, and R⁵ to R¹¹ may each be defined identically ordifferently and be covalently joined together, and each be F, Cl, Br, I,—CF₃, —OR¹², —COR¹², —CO₂R¹², —CO₂M, —SR¹², —SO₂R¹², —SOR¹², —SO₃R¹²,—SO₃M, —SO₂NR¹²R¹³, NR¹²R¹³, N⁺R¹²R¹³R¹³, N═CR¹²R¹³, NH₂, where R¹²,R¹³=H, substituted or unsubstituted, aliphatic or aromatic hydrocarbonradicals having from 1 to 25 carbon atoms, each defined identically ordifferently, and M=alkali metal, alkaline earth metal, ammonium,phosphonium ion.

Specific embodiments of the N-phenylpyrrolebisphosphines according tothe invention relate to phosphines of the formulae II, III, IV and V

where each of the radical pairs R⁵ and R⁶, R⁶ and R⁷, R⁷ and R⁸ or R⁹and R¹⁰ together are a fused aromatic which is optionally likewisesubstituted.

The substituents of the additional aromatic system R¹⁴, R¹⁵, R¹⁶ and R¹⁷may each be H, an aliphatic, alicyclic, aliphatic-alicyclic,heterocyclic, aliphatic-heterocyclic, aromatic, aromatic-aromatic,aliphatic-aromatic hydrocarbon radical having from 1 to 50 carbon atoms,and R¹⁴ to R¹⁷ may each be defined identically or differently and becovalently joined together, and each be F, Cl, Br, I, −Si(CH₃)₃, —CF₃,—OR¹², —COR¹², —CO₂R¹², —CO₂M, —SR¹², —SO₂R¹², —SOR¹², —SO₃R¹², —SO₃M,—SO₂NR¹²R¹³, NR¹²R¹³, N⁺R¹²R¹³R¹³, N═CR¹²R¹³, NH₂, where R¹², R¹³=H,substituted or unsubstituted, aliphatic or aromatic hydrocarbon radicalshaving from 1 to 25 carbon atoms, each defined identically ordifferently, and M=alkali metal, alkaline earth metal, ammonium,phosphonium ion.

R¹, R², R³, R⁴, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰ and R¹¹ in the formulae II, III,IV and V are as defined in claim 1 or for formula I, and R¹ to R⁴ and R⁵to R¹¹ may in each case be defined identically or differently.

The aliphatic, cycloaliphatic or aromatic hydrocarbon radicals maycontain heteroatoms, for example nitrogen, oxygen or sulfur, andoptionally bear one or more substituents, for example halogen atoms.Examples of R¹–R⁴ are phenyl, m-sulfonatophenyl, p-fluorophenyl,o-fluorophenyl, m-fluorophenyl, p-methoxyphenyl, o-methoxyphenyl,m-methoxyphenyl, 1-naphthyl, 2-naphthyl, methyl, ethyl, n-propyl,i-propyl, n-butyl, s-butyl, i-butyl, hexyl, cyclohexyl, adamantyl.Examples in which R¹ and R² and/or R³ and R⁴ have one or more covalentbonds are 1,1′-diphenyl-2,2′-diyl, cyclooctane-1,5-diyl. R¹ to R⁴ arepreferably substituted or unsubstituted phenyl, cyclohexyl and adamantylgroups.

When the rotation around the N-phenyl bond is restricted, some of thecompounds according to the invention are enantiomers as a consequence ofaxial chirality, and, in the event of additional chirality in theradicals R¹–R¹¹, diastereomers.

In preferred embodiments of the invention, theN-phenylpyrrolebisphosphines are chiral, and preference is given to oneor more of the radicals R¹ to R¹¹ being chiral. Particular preference isgiven to chiral substituents for R¹–R⁴. Examples of such chiral groupsare menthyl, camphyl, 1,1′-binaphth-2-yl, hexane-2,5-diyl.

The use of one or more chiral radicals in R¹ to R¹¹ offers theadvantage, inter alia, that when there is axial chirality (N-phenyl bondas the chirality axis), the diastereomers can be easily separated.

The invention therefore relates both to mixtures of individualenantiomers and diastereomers of the N-phenylpyrrolebisphosphine ligandsaccording to the invention and to the individual enantiomers ordiastereomers themselves and their use in enantioselective ordiastereoselective catalytic reactions.

The present invention further provides N-phenylpyrrolebisphosphine-metalcomplexes containing a transition group metal of the 1st, 2nd, 3rd, 4th,5th, 6th, 7th or 8th transition group of the Periodic Table, theelements of the lanthanides and/or actinides and one or moreN-phenylpyrrolebisphosphines of the formulae I, II, III, IV or V. Thesubstituents (R¹–R¹⁷) of these N-phenylpyrrolebisphosphines are asalready defined. Metals used with preference are Ti, Zr, Cr, Mo, W, Mn,Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag and Zn. Particularpreference is given to the metals of the 8th transition group of thePeriodic Table.

The remarks of all embodiments of the N-phenylpyrrolebisphosphines ofthe formulae I to V apply correspondingly to the metal complexes. Whenthe N-phenylpyrrolebisphosphine ligands are chiral as described, themetal complexes may have one, more than one or exclusively chiralN-phenylpyrrolebisphosphine ligands.

Representative examples of ligands of the general formulae I, II, III,IV and V for the purposes of this invention are depicted hereinbelow,without limiting the scope of protection of the present invention.

I-a

I-b

I-c

I-d

I-f

I-g

I-h

I-i

I-j

I-k

II-a

III-a

IV-a

IV-b

IV-c

V-a

V-b

V-c

V-d

The N-phenylpyrrolebisphosphines according to the invention can beobtained by various synthetic routes. A simple route is the doublemetalation of N-phenylpyrroles and the subsequent reaction with thephosphorus component (R³═R¹, R⁴═R²).

The radicals R⁵–R¹¹ can be introduced even after attachment of thephosphorus groups. This route was taken, for example, in the synthesisof compound I-h:

Ligands occurring in racemic form can be separated into the opticalisomers by literature routes, for example chromatographically on chiralsupports or as diastereomers after reaction with chiral auxiliaries andsubsequent dissociation.

The N-phenylpyrrolebisphosphines according to the invention of theformulae I, II, III, IV and V are notable for a high hydrolysisstability. They are especially soluble in the common organic solvents.When one or more groups R1 to R11 or R14 to R17 or one or moresubstituents R1 to R4 bears a strongly polar radical (for example asulfonic acid group), the solubility falls in nonpolar organic solvents,while at the same time rising in polar solvents, for example water. TheN-phenylpyrrolebisphosphines according to the invention and their metalcomplexes may therefore be soluble even in water or polar organicsolvents.

As a consequence of their high molecular weight, theN-phenylpyrrolebisphosphines according to the invention have a lowvolatility. They can therefore easily be removed from more volatilereaction products.

The invention further provides the use of theN-phenylpyrrolebisphosphines or their metal complexes in hydrogenations,isomerizations, carbonylations, carboxylations, hydroformylations,hydrocyanations, cyclopropanations, C—C couplings, oligomerizations orpolymerizations.

The N-phenylpyrrolebisphosphines according to the invention of theformulae I, II, III, IV and V are suitable building blocks for thepreparation of complexes with metals of the 1st to 8th transition groupof the Periodic Table, the lanthanides and/or the actinides. Especiallywith metals of the 6th to 8th transition group, these complexes can beused as catalysts for hydrogenations, isomerizations, carbonylations,carboxylations, hydroformylations, hydrocyanations, cyclopropanations,C—C coupling reactions, oligomerizations and polymerizations. Preferredfields of use are hydrogenations, hydroformylations and C—C couplingreactions.

When the N-phenylpyrrolebisphosphines according to the invention of theformulae I to V are used, optionally as the metal complex, inhydrogenations, preference is given to using metals of the 8thtransition group of the Periodic Table. The substrates used arepreferably compounds having double bonds, for example C═C, C═O or C═Ndouble bonds which are hydrogenated to a single bond. Examples ofhydrogenations can be found, for example, in Matthias Beller, CarstenBolm (Ed.) “Transition Metals for Organic Synthesis”, Wiley-VCH,Weinheim, New York, Chichester, Brisbane, Singapore, Toronto, 1998, Vol.2, pages 3–80.

When the N-phenylpyrrolebisphosphines according to the invention of theformulae I to V are used, optionally as a metal complex, inhydroformylations, preference is given to using metals of the 8thtransition group of the Periodic Table. Especially when rhodium is usedas the catalyst metal, high catalytic activities are obtained in thehydroformylations. The reactants used in these hydroformylations arepreferably olefins having from 2 to 25 carbon atoms, for example butenes(1-butene, 2-butene, i-butene), octenes (1-octene, dibutenes), dodecenes(tributenes).

When the N-phenylpyrrolebisphosphines according to the invention of theformulae I to V are used, optionally as the metal complex, in C—Ccoupling reactions, preference is given to using metals of the 8thtransition group of the Periodic Table, more particularly of nickel andpalladium. Examples of C—C coupling reactions can be found, for example,in Matthias Beller, Carsten Bolm (Ed.) “Transition Metals for OrganicSynthesis”, Wiley-VCH, Weinheim, New York, Chichester, Brisbane,Singapore, Toronto, 1998, Vol. 1, pages 208–240.

In the metal-catalyzed reactions, either theN-phenylpyrrolebisphosphine-metal complexes, optionally with additional,free ligand, or the N-phenylpyrrolebisphosphines and a metal compoundfrom which the catalyst complex forms with theN-phenylpyrrolebisphosphines under the reaction conditions are used.

When the N-phenylpyrrolebisphosphine compounds according to theinvention and/or their metal complexes are used in metal-catalyzedreactions, the ratio of ligand to metal (mol/mol) is from 1:2 to 200:1,preferably from 1:1 to 1:50, more preferably from 1:1 to 1:20. Ligand orligand-metal complex are generally dissolved homogeneously in one ormore of the liquid phases present. It is also possible to use theN-phenylpyrrolebisphosphines in supported aqueous phase catalysts.

The examples which follow are intended to illustrate the invention, butnot to restrict the scope of application as evident from the patentclaims.

EXAMPLES

All operations are carried out under argon by means of Schlenktechniques with dried and degassed solvents.

Example 1 1-(2-Diphenylphosphinophenyl)pyrrole-2-diphenylphosphine (I-a,JaPHOS)

1.52 g (10.6 mmol) of N-phenylpyrrole are dissolved in 50 ml of Et₂O ina 250 ml three-neck flask (equipped with magnetic stirring) and admixedwith 2.5 g (3.2 ml) of TMEDA (tetramethylethylenediamine). At 25° C.,13.6 ml of 1.6 molar n-butyllithium solution (21.2 mmol) aresubsequently added. The reaction mixture is stirred at room temperaturefor 12 h. This reaction solution I is transferred to a dropping funnel.4.68 g (21.23 mmol) of diphenylchlorophosphine are mixed with 50 ml ofether in a 250 ml three-neck flask. This solution II is cooled to 0° C.Solution I of the dilithiated N-phenylpyrrole is slowly added dropwiseat 20° C. to this solution II. Stirring is subsequently continued atroom temperature for 1 h. The reaction solution is admixed with 20 ml ofwater and stirred for 10 min. The phases are separated and the organicphase is dried over sodium sulfate for 12 h. This is subsequentlyconcentrated under reduced pressure and the residue is dissolved in 20ml of toluene. This solution is cautiously covered with 100 ml ofhexane. The target product crystallizes out within one day. It isfiltered and dried under reduced pressure.

Yield: 4.88 g (90% of theory); M=511.54 g/mol

³¹P NMR:(δ[ppm], J[Hz], CDCl₃): −17.5 d, J_(PP)=18; −30.7 d, J_(PP)=18

¹H NMR: (δ[ppm], J[Hz], CDCl₃): 6.01 d,d, J=3.6, J=3.6 (1H); 6.11 d, d,J=3.57, J=3.57 (1H); 6.58 m (1H), 7.0 m(4H); 7.1–7.3 m (20H)

¹³C NMR: (δ[ppm], J[Hz], CDCl₃): 108.9 s; 118.9 s; 128–129 m; 130.0 d,J=3; 133–134 m; 34.8 d, J=2.8; 136.9 s; 137.0 d, J=2; 137.3 d, J=13.3;137.7 d, ¹J_(PC)=17.16; 137.8 d, ¹J_(PC)=15.2; 144.4 d, ¹J_(PC)=26;144.7 d, ¹J_(PC)=26

MS, m/z (%): 511(1)[M⁺], 434(7)[M⁺-Ph], 326(100)[M⁺-PPh₂],249(10)[M⁺-PPh₂-Ph], 183(15)[PPh₂], 172(8)[M⁺-PPh₂-2Ph]; EA: calc.:C:79.8, H:5.32, N:2.7; found: C:79.9, H:5.5, N:2.5.

Example 21-(2-Dicyclohexylphosphinophenyl)pyrrole-2-dicyclohexylphosphine (I-b,Cyc-JaPHOS)

0.43 g (3.04 mmol) of N-phenylpyrrole are dissolved in 20 ml of Et₂O ina 50 ml three-neck flask (equipped with magnetic stirring) and admixedwith 0.704 g (0.91 ml) of TMEDA (tetramethylethylenediamine). At 25° C.,3.8 ml of 1.6 molar n-butyllithium solution (6.06 mmol) are subsequentlyadded. The reaction mixture is stirred at room temperature for 12 h.This reaction solution I is transferred to a dropping funnel. 1.41 g(6.06 mmol) of dicyclohexylchlorophosphine are mixed with 20 ml of Et₂Oin a 100 ml three-neck flask. This solution II is cooled to 0° C.Solution I of the dilithiated N-phenylpyrrole is added dropwise at 0° C.to the solution II. The mixture is subsequently stirred at 25° C. for 1h. The reaction solution is admixed with 20 ml of water and stirred for10 min. The phases are separated and the organic phase is dried oversodium sulfate for 12 h. This is subsequently concentrated under reducedpressure and the residue is dissolved in 200 ml of hot ethanol. Thetarget product crystallizes out within one day. It is filtered and driedunder reduced pressure.

Yield: 1.2 g (74% of theory); M=535.73 g/mol

³¹P NMR:(δ[ppm], J[Hz], CDCl₃): 15.9 d, J_(PP)=6.94; −28.1 d,J_(PP)=6.94

¹H NMR: (δ[ppm], J[Hz], CDCl₃): 0.9–1.2 m(21H); 1.5–1.8 m (23H); 6.27d,d, J=2.57, J=2.58 (1H); 6.45 d,d, J=1.59, J=1.58(1H); 6.7 m(1H); 7.1m(1H); 7.2–7.3 m(2H); 7.4–7.5 m (1H)

¹³C NMR: (δ[ppm], J[Hz], CDCl₃): 26.4 d, J=10.5; 26.7 d, J=8.6;27.0–27.6 m; 28.6 d, J=5.8; 29.7 d, J=11.4; 29.8 d, J=15; 30.5 d, J=19;30.9, 31 d,d J=15; 31.4, 31.45 d,d, J=16; 34.6 d, J=26.7; 34.8 d,J=19.1; 35.4 d, J=9.54; 36.1 d, J=16.2; 107.6 s; 116 d, J=3.8; 127 s;127.5 s; 128.1 s; 129.5 d, J=6.7; 130.0 d,d, J=3.8; 133.0 d, J=3.8;135.4 d, ¹J_(PC)=22; 147.01, 147.0 d,d, ¹J_(PC)=24.8

MS, m/z (%): 535 (2)[M⁺], 452 (100) [M⁺-Cy], 369 (7) [M⁺-2Cy],338(5)[M⁺-PCy₂], 204 (7)[M⁺-4Cy]; 83 (5)[Cy], EA: calc.: C:76.2, H:9.6,N:2.6; found: C:75.9, H:9.5, N:2.6.

Example 3 1-(2-Diadamantylphosphinophenyl)pyrrole-2-diadamantylphosphine(I-c, Ad-JaPHOS)

0.32 g (2.2 mmol) of N-phenylpyrrole are dissolved in 20 ml of Et₂O in a50 ml three-neck flask (equipped with magnetic stirring) and admixedwith 0.5 g (0.75 ml) of TMEDA (tetramethylethylenediamine). At 25° C.,2.8 ml of 1.6 molar n-butyllithium solution (4.4 mmol) are subsequentlyadded. The reaction mixture is stirred at 25° C. for 12 h. This reactionsolution I is transferred to a dropping funnel. 1.5 g (4.4 mmol) ofdiadamantylchlorophosphine are mixed with 40 ml of THF in a 100 mlthree-neck flask. This solution II is cooled to 0° C. Solution I isadded dropwise at 0° C. to the solution II. Subsequently, the mixture isheated and stirred under reflux (approximately 60° C.) for 36 h. Thereaction solution is concentrated under reduced pressure, and theresidue is dissolved with 20 ml of toluene, admixed with 20 ml of waterand stirred for 10 min. The phases are separated and the organic phaseis dried over a little dry sodium sulfate for 12 h. After filtration,100 ml of ethanol are added.

The colorless target product crystallizes out within day. It is filteredand dried under reduced pressure.

Yield: 0.25 g (15.3% of theory); M=744.03 g/mol

³¹P NMR:(δ[ppm], J[Hz], CDCl₃): 17.81 d, J=5.5; 4.75 d, J=5.5

¹H NMR: (δ[ppm], J[Hz], CDCl₃): 1.5–2.0 m (60H); 6.2 t, J=3:1 (1H); 6.6d,d J=1.5, J=3.6 (1H) 6.9 m (1H); 7.1 m (1H); 7.2 m (2H); 7.8 m (1H)

MS, m/z (%): 744 (3)[M⁺], 608 (60)[M⁺-Ad], 442 (2) [M⁺-PAd₂],301(2)[PAd₂], 135 (100) [Ad]

Examples 4–7 General Procedure 1 (GP 1) for Synthesis of Rhodium (I)-NBDor COD Complexes with Cyc-JaPHOS and JaPhOS as Ligands

1 mmol of Rh(NBD)(acac) or Rh(COD) (acac) is dissolved in 10 ml. of THFand cooled to −70° C. 1 mmol of ligand from Example 1–2 dissolved in 40ml of THF is added dropwise to the rhodium solution within 10 minutes.The solution is heated to room temperature with magnetic stirring andadmixed with 120 μl of 54% HBF₄ (solution in ether). Subsequently,precipitation is effected using 20 ml of Et₂O, followed by filtering andwashing with Et₂O. The yields are over 90%. The analytical data of thecompounds prepared by GP 1 are compiled in Table 1.

TABLE 1 Analytical data of the complexes of Examples 4–8 (NMR[MeOD-d4],δ[ppm], J[Hz], MS Intectra AMD 402, FAB positive using NBA as thematrix) Ex. Yield No. Formula [%] ³¹P NMR ¹H NMR MS, m/z (%): 4Rh(I)(Cyc-JaPHOS)(COD)⁺BF₄ ⁻

94 24.4 d,d;²J_(PP) = 24.9;¹J_(PRh) = 130.418.7 d,d;²J_(PP) =24,9;¹J_(PRh) = 145.65 0.5–2.5 m(Cy;44 H,COD,8H),4.5 bs (1H, COD)4.7bs(1H,COD)4.9 bs (1H, COD)5.8 bs (1H,COD)6.45 d,d, J = 1.59,J = 1.58(1H)6.9 m (1H)7.2 m (2H)7.5 m (2H)7.9 m (1H) 746 (100)[Rh(Cyc-JaPHOS)(COD)]⁺;637 (70) [Rh(Cyc-JaPHOS)(COD)]⁺-NBD 5Rh(I)(Cyc-JaPHOS)(NBD)⁺BF₄ ⁻

90 25.1 d of m,¹J_(PRh) = 15411.1 d of m¹J_(PRh) = 131.8 0.8–2.1 m (Cy,44H,NBD,2H);3.9 bs (1H, NBD)4.1 bs (1H,NBD)4.8 bs (1H, COD)5.1–5.3m(3H,NBD)6.5 d,d, m(1H)6.9 m (1H) 7.2 m (1H)7.5 m (1H)7.9 m (3H) 730(100) [Rh(Cyc-JaPHOS)(NBD)]⁺;637 (80) [Rh(Cyc-JaPHOS)(NBD)]⁺-NBD 6Rh(I)(JaPHOS)(COD)⁺BF₄ ⁻

93 21.3 d,d;²J_(PP) = 37.5;¹J_(PRh) = 148.4318.1 d,d;²J_(PP) =37.5;¹J_(PRh) = 147.0 2.0 m (4H, COD)2.5–2.7m(4H, COD)4.55 m (2H,COD)4.7m (2H, COD)5.75 m (1H) 6.21 m (1H)6.44 m (1H)6.55 m (1H)7.05 m(2H)7.2–7.5 (18H)7.68 d,J = 6.9 (1H)7.69 d,J = 6.9 (1H)7.8 d,J = 7.6(1H);7.81 d,J = 7.63 (1H) 722 (100[Rh(Cyc-JaPHOS)(COD)]⁺;614 (75)[Rh(Cyc-JaPHOS)(COD)]⁺-COD 7 Rh(I)(JaPHOS)(NBD)⁺BF₄ ⁻

91 22.7 d,d;²Jphd PP = 38.84;¹J_(PRh) = 158.1418.7 d,d;²J_(PP) =38.84;¹J_(PRh) = 156.75 1.5 bs (2H, NBD)4.0 bs (2H, NBD)4.55 bs(1H,NBD)4.65 bs (1H,NBD)5.0 bs (1H, NBD)5.2 bs (1H, NBD) 5.75 m (1H)6.2m (1H)6.3 m (1H)6.55 m (1H)7.05 m (2H)7.2–7.5 (18H)7.7 d,J = 6.9(1H)7.71 d,J = 6.9 (1H)7.9 d,J = 7.6 (1H)7.91 d,J = 7.63 (1H) 706(100)[Rh(JaPHOS)(NBD)]⁺; 614 (45)[Rh(JaPHOS)(COD)]⁺-NBD

Example 8 Hydroformylation Reaction of 1- or cis/trans-2-pentene Using aRhodium/JaPHOS Catalyst

A mixture of 73 mmol of alkene, the corresponding amount ofRh(acac)(CO)₂ as a catalyst precursor (0.01 mol % of catalyst, 0.0073mmol=1.88 mg), the corresponding amount of JaPHOS, 2 ml of isooctane asan internal standard and also 30 ml of anisole as a solvent is reactedin a Parr 100 ml autoclave (with magnetic stirring). The synthesis gaspressure (H₂/CO=1:1) is kept constant at the specified value once theworking pressure is obtained. After the reaction time, completion ofcooling and decompression of the autoclave, the reaction mixture isanalyzed by gas chromatography (results see Table 2).

TABLE 2 Hydroformylation results of 1- or cis/trans-2-pentene using arhodium/JaPHOS catalyst Rh Rh:JaPHOS T P T Yield^(a) Substrate [mol %][mol/mol] [° C.] [bar] [h] [%] n:iso^(b) 1-Pentene 0.01 1:5 120 50 6 9447:53 2-Pentene^(c) 0.01 1:5 120 50 6 54 24:76 2-Pentene^(c) 0.01 1:5120 25 6 25 39:61 ^(a)Yield = 1-hexanal + 2-methylpentanal +2-ethylbutanal, ^(b)n:iso = 1-hexanal:2-methylpentanal + 2-ethylbutanal,[mol:mol] ^(c)2-pentene = cis/trans-2-pentene

Example 9 General Procedure for Hydrogenating Olefins by Means ofCatalysis Using Rhodium/N-phenylpyrrolylbisphosphine Catalysts fromExample 4–7: (GP 3)

0.01 mmol (or less) of the appropriate complex from Example 4–7 ismelted in a glass ampule and introduced under argon into a thermostatedhydrogenation vessel (equipped with magnetic stirring). Subsequently, 15ml of methanol and 1 mmol of substrate are added. After gas exchange ofargon for hydrogen, the reaction is started by destroying the glassampule of the precatalyst. During the reaction, the temperature is keptconstant at 25° C. and the hydrogen pressure at 1 bar, and the gasconsumption is measured using automatic registering apparatus. The timeto complete conversion of the substrate is measured. The product issubsequently analyzed by GC. Example see Table 3.

TABLE 3 Hydrogenation results for hydrogenating olefins by means ofcatalysis using rhodium/N-phenylpyrrolylbisphosphine catalystsPrecatalyst Substrate (mmol) (mmol) t1 t2 Rh(I)(JaPHOS)(COD)⁺BF₄ ⁻COD^(a) COD→COE^(b) COE→COA^(c) (0.01) (1)  4.7 h  3 dRh(I)(JaPHOS)(NBD)⁺BF₄ ⁻ NBD^(d) NBD^(d)→NBE^(e) NBE^(e)→NBA^(f) (0.01)(1)  2.5 min 40 min Rh(I)(Cyc-JaPHOS)(COD)⁺BF₄ ⁻ COD^(a) COD→COE^(b)COE→COA^(c) (0.01) (1) 100 min 10 min Rh(I)(Cyc-JaPHOS)(NBD)⁺BF₄ ⁻NBD^(d) NBD^(d)→NBE^(e) NBE^(e)→NBA^(f) (0.0007) (1)  2.5 min 40 min^(a) = 1,4-cyclooctadiene, ^(b) = cyclooctene, ^(c) = cyclooctane, ^(d)= 2,5-norbornadiene, ^(e) = 2-norbornene, ^(f) = norbornane

1. An N-phenylpyrrolebisphosphine of formula I

where R¹, R², R³, R⁴ are selected from the group consisting ofaliphatic, cycloaliphatic and aromatic hydrocarbon radicals having from1 to 25 carbon atoms, and R¹ and R² and/or R³ and R⁴ may be joined byone or more covalent bonds, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ are selectedfrom the group consisting of H, aliphatic, alicyclic,aliphatic-alicyclic, heterocyclic, aliphatic-heterocyclic, aromatic,aromatic-aromatic, and aliphaticaromatic hydrocarbon radicals havingfrom 1 to 50 carbon atoms, and R⁵ to R¹¹ may each be defined identicallyor differently and be covalently joined together, and each are selectedfrom the group consisting of F, Cl, Br, I, —Si(CH₃)₃, —CF₃, —OR¹²,—COR¹², —CO₂R¹², —CO₂M, —SR¹², —SO₂R¹², —SOR¹², —SO₃R¹², —SO₃M,—SO₂NR¹²R¹³, NR¹²R¹³, N⁺R¹²R¹³R¹³, and N═CR¹²R¹³, NH₂, where R¹², R¹³ isselected from the group consisting of H, substituted or unsubstitutedaliphatic and aromatic hydrocarbon radicals having from 1 to 25 carbonatoms, each defined identically or differently, and M is selected fromthe group consisting of alkali metal, alkaline earth metal, ammonium,and phosphonium ion.
 2. An N-phenylpyrrolebisphosphine as claimed inclaim 1, wherein R⁵ and R⁶ together are a fused aromatic in formula II

where R¹⁴, R¹⁵, R¹⁶, R¹⁷ are the same or different and are selected fromthe group consisting of H, aliphatic, alicyclic, aliphatic-alicyclic,heterocyclic, aliphatic-heterocyclic, aromatic, aromatic-aromatic,aliphatic-aromatic hydrocarbon radicals having from 1 to 50 carbonatoms, F, Cl, Br, I, —Si(CH₃)₃, —CF₃, —OR¹², —COR¹², —CO₂R¹², —CO₂M,—SR¹², —SO₂R¹², —SOR¹², —SO₃R¹², —SO₃M, —SO₂NR¹²R¹³, NR¹²R¹³,N⁺R¹²R¹³R¹³, N═CR¹²R¹³, and NH₂, where R¹², R¹³ are selected from thegroup consisting of H, substituted or unsubstituted aliphatic andaromatic hydrocarbon radicals having from 1 to 25 carbon atoms, eachdefined identically or differently, and M is selected from the groupconsisting of alkali metal, alkaline earth metal, anmonium andphosphonium ion.
 3. An N-phenylpyrrolebisphosphine as claimed in claim1, wherein R⁶ and R⁷ together are a fused aromatic in formula III

where R¹⁴, R¹⁵, R¹⁶, R¹⁷ are selected from the group consisting of H,aliphatic, alicyclic, aliphatic-alicyclic, heterocyclic,aliphatic-heterocyclic, aromatic, aromatic-aromatic, aliphatic-aromatichydrocarbon radicals having from 1 to 50 carbon atoms, F, Cl, Br, I,—Si(CH₃)₃, —CF₃, —OR¹², —COR¹², —CO²R¹², —CO²M, —SR¹², —SO²R¹², —SOR¹²,—SO₃R¹², —SO³M, —SO₂NR¹²R¹³, NR¹²R¹³, NR¹²R¹³R¹³, N═CR¹²R¹³, and NH₂,where R¹², R¹³ are selected from the group consisting of H, substitutedor unsubstituted aliphatic and aromatic hydrocarbon radicals having from1 to 25 carbon atoms, each defined identically or differently, and M isselected from the group consisting of alkali metal, alkaline earthmetal, ammonium, and phosphonium ion.
 4. An N-phenylpyrrolebisphosphineas claimed in claim 1, wherein R⁷ and R⁸ together are a fused aromaticin formula IV

where R¹⁴, R¹⁵, R¹⁶, R¹⁷ are selected from the group consisting of H,aliphatic, alicyclic, aliphatic-alicyclic, heterocyclic,aliphatic-heterocyclic, aromatic, aromatic-aromatic, aliphatic-aromatichydrocarbon radicals having from 1 to 50 carbon atoms, F, Cl, Br, I,—Si(CH³)³, —CF³, —OR¹², —COR¹², —COR₂R¹², —CO₂M, —SR¹², —SO₂R¹², —SOR¹²,—SO₃R¹², —SO₃M, —SO₂NR¹²R¹³, NR¹²R¹³, N⁺R¹²R¹³R¹³, N═CR¹²R¹³, and NH₂,where R¹², R¹³ are selected from the group consisting of H, substitutedor unsubstituted aliphatic and aromatic hydrocarbon radicals having from1 to 25 carbon atoms, each defined identically or differently, and M isselected from the group consisting of alkali metal, alkaline earthmetal, ammonium, and phosphonium ion.
 5. An N-phenylpyrrolebisphosphineas claimed in claim 1, wherein R⁹ and R¹⁰ together are a fused aromaticin formula V

where R¹⁴, R¹⁵, R¹⁶, R¹⁷ are selected from the group consisting of H,aliphatic, alicyclic, aliphatic-alicyclic, heterocyclic,aliphatic-heterocyclic, aromatic, aromatic-aromatic, aliphatic-aromatichydrocarbon radicals having from 1 to 50 carbon atoms, F, Cl, Br, I,—Si(CH₃)₃, —CF₃, —OR¹², —COR¹², —CO₂R², —CO₂M, —SR¹², —SO₂R¹², —SOR¹²,—SO₃R¹², —SO₃M, —SO₂NR¹²R¹³, NR¹²R¹³, N⁺R¹²R¹³R¹³, N═CR¹²R¹³, and NH₂,where R¹², R¹³ are selected from the group consisting of H, substitutedor unsubstituted aliphatic and aromatic hydrocarbon radicals having from1 to 25 carbon atoms, each defined identically or differently, andM=alkali metal, alkaline earth metal, ammonium, and phosphonium ion. 6.An N-phenylpyrrolebisphosphine as claimed in claim 1, which is chiral.7. An N-phenylpyrrolebisphosphine as claimed in claim 1, wherein one ormore of the radicals R¹–R⁴ or R¹ and R² and/or R³ and R⁴ together are achiral radical selected from the group consisting of menthyl, eamphyl,1,1′-binaphth-2-yl, and hexane-2,5-diyl.
 8. AnN-phenylpyrrolebisphosphine-metal complex comprising a metal of the 1st,2nd, 3rd, 4th, 5th, 6th, 7th or 8th transition group of the PeriodicTable of the Elements, or an element from the lanthanides and/oractinides and one or more N-phenylpyrrolebisphosphines of formula I

where R¹, R², R³, R⁴ are selected from the group consisting ofaliphatic, cycloaliphatic and aromatic hydrocarbon radicals having 1 to25 carbon atoms, R⁵, R⁶, R⁷, R⁸, R⁹, R¹⁰, R¹¹ are selected from thegroup consisting of H, aliphatic, alicyclic, aliphatic-alicyclic,heterocyclic, aliphatic-heterocyclic, aromatic, aromatic-aromatic, andaliphaticaromatic hydrocarbon radicals having from 1 to 50 carbon atoms,and R⁵ to R¹¹ may each be defined identically or differently and becovalently joined together, and each are selected from the groupconsisting of F, Cl, Br, I, —Si(CH₃)₃, —CF, —OR¹¹, —COR¹², —CO₂R¹²,—CO₂M, —SR¹², —SO₂R¹², —SOR¹², —SO₃R¹², —SO₃M, —SO₂NR¹²R¹³, NR¹²R¹³,N+R¹²R¹³R¹³, N═CR¹²R¹³, and NH₂, where R¹², R¹³ are selected from thegroup consisting of H, substituted or unsubstituted aliphatic andaromatic hydrocarbon radicals having from 1 to 25 carbon atoms, eachdefined identically or differently, and M is selected from the groupconsisting of alkali metal, alkaline earth metal, ammonium, andphosphonium ion.
 9. An N-phenylpyrrolebisphosphine-metal complex asclaimed in claim 8, wherein R⁵ and R⁶ together are a fused aromatic informula II

where R¹⁴, R¹⁵, R¹⁶, R¹⁷ are selected from the group consisting of H,aliphatic, alicyclic, aliphatic-alicyclic, heterocyclic,aliphatic-heterocyclic, aromatic, aromatic-aromatic, aliphatic-aromatichydrocarbon radicals having from 1 to 50 carbon atoms, F, Cl, Br, I,—Si(CH₃)₃, —CF₃, —OR¹², —COR¹², —CO₂R¹², —CO₂M, —SR¹², —SO₂R¹², —SO₃R¹²,SO₃M, —SO₂NR¹²R¹³, NR¹²R¹³, N⁺R¹²R¹³R¹³, N═CR¹²R¹³, and NH₂, whereR¹²,R¹³ are selected from the group consisting of H, substituted orunsubstituted aliphatic and aromatic hydrocarbon radicals having from 1to 25 carbon atoms, each defined identically or differently, and M isselected from the group consisting of alkali metal, alkaline earthmetal, ammonium, and phosphonium ion and one or more of the radicalsR¹–R⁴ or R¹and R² and/or R³ and R⁴ together are a chiral radicalselected from the group consisting of menthyl, camphyl,1,1′-binaphth-2-yl, and hexane-2,5-diyl.
 10. AnN-phenylpyrrolebisphosphine-metal complex as claimed in claim 8, whereinR⁶ and R⁷ together are a fused aromatic in formula III

where R¹⁴, R¹⁵, R¹⁶, R¹⁷ are selected from the group consisting of H,aliphatic, alicyclic, aliphatic-alicyclic, heterocyclic,aliphatic-heterocyclic, aromatic, aromatic-aromatic, aliphatic-aromatichydrocarbon radicals having from 1 to 50 carbon atoms, F, Cl, Br, I,—Si(CH₃)₃, —CF₃, —OR¹², —COR¹², —CO₂R¹², —CO₂M, —SR¹², —SO₂R¹² , —SOR¹²,—SO₃R¹², —SO₃M, —SO₂NR¹²R¹³, NR¹²R¹³, N⁺R¹² R¹³R¹³, N═CR¹²R¹³, and NH₂,where R¹², R¹³ are selected from the group consisting of H, substitutedor unsubstituted aliphatic and aromatic hydrocarbon radicals having from1 to 25 carbon atoms, each defined identically or differently, and M isselected from the group consisting of alkali metal, alkaline earthmetal, ammonium, and phosphonium ion and one or more of the radicalsR¹–R⁴ or R¹ and R² and/or R³ and R⁴ together are a chiral radicalselected from the group consisting of menthyl, camphyl,1,1′-binaphth-2-yl, and hexane-2,5-diyl.
 11. AnN-phenylpyrrolebisphosphine-metal complex as claimed in claim 8, whereinR⁷ and R⁸ together are a fused aromatic in formula IV

where R¹⁴, R¹⁵, R¹⁶, R¹⁷ are selected from the group consisting of H,aliphatic, alicyclic, aliphatic-alicyclic, heterocyclic,aliphatic-heterocyclic, aromatic, aromatic-aromatic, aliphatic-aromatichydrocarbon radicals having from 1 to 50 carbon atoms, F, Cl, Br, I,—Si(CH₃)₃, —CF₃, —OR¹², —COR¹², —CO₂R¹², —CO₂M, —SR¹², —SO₂R¹², —SOR¹²,—SO₃R¹², —SO₃M, —SO₂NR¹²R¹³, NR¹²R¹³, N⁺R¹²R¹³R¹³, N═CR¹²R¹³, NH₂, whereR¹², R¹³ are selected from the group consisting of H, substituted orunsubstituted aliphatic and aromatic hydrocarbon radicals having from 1to 25 carbon atoms, each defined identically or differently, and M isselected from the group consisting of alkali metal, alkaline earthmetal, ammonium, and phosphonium ion and one or more of the radicalsR¹–R⁴ or R¹ and R² and/or R³ and R⁴ together are a chiral radicalselected from the group consisting of menthyl, camphyl,1,1′-binaphth-2-yl, and hexane-2,5-diyl.
 12. AnN-phenylpyrrolebisphosphine-metal complex as claimed in claim 8, whereinR⁹ and R¹⁰ together are a fused aromatic in formula V

where R¹⁴, R¹⁵, R¹⁶, R¹⁷ are selected from the group consisting of H,aliphatic, alicyclic, aliphatic-alicyclic, heterocyclic,aliphatic-heterocyclic, aromatic, aromatic-aromatic, aliphatic-aromatichydrocarbon radicals having from 1 to 50 carbon atoms, F, Cl, Br, I,—Si(CH₃)₃, —CF₃, —OR¹², —COR¹², —CO₂R¹², —CO₂M, —SR¹², —SO₂R¹², —SOR¹²,—SO₃R¹², —SO₃M, —SO₂NR¹²R¹³, NR¹²R¹³, N⁺R¹²R¹³R¹³, N═CR¹²R¹³, NH₂, whereR¹², R¹³ are selected from the group consisting of H, substituted orunsubstituted aliphatic and aromatic hydrocarbon radicals having from 1to 25 carbon atoms, each defined identically or differently, and M isselected from the group consisting of alkali metal, alkaline earthmetal, ammonium, and phosphonium ion and one or more of the radicalsR¹–R⁴ or R¹ and R² and/or R³ and R⁴ together are a chiral radicalselected from the group consisting of menthyl, camphyl,1,1′-binaphth-2-yl, and hexane-2,5-diyl.
 13. AnN-phenylpyrrolebisphosphine-metal complex as claimed in claim 8, whereinone or more of the N-phenylpyrrolebisphosphine ligands present in thecomplex is chiral.
 14. An N-phenylpyrrolebisphosphine-metal complex asclaimed in claim 8, wherein one or more of the radicals R¹–R⁴ or R¹ andR² and/or R³ and R⁴ of one or more N-phenylpyrrolebisphosphine ligandspresent in the complex together are a chiral radical selected from thegroup consisting of menthyl, camphyl, 1,1′-binaphth-2-yl, andhexane-2,5-diyl.
 15. An N-phenylpyrrolebisphosphine-metal complex asclaimed in claim 8, wherein the metal is a metal of the 8th transitiongroup of the Periodic Table.
 16. A method comprising: reacting at leastone olefin with N-phenylpyrrolebisphosphine as claimed in claim 1,wherein said reacting is selected from the group consisting ofhydrogenation, isomerization, carbonylation, carboxylation,hydroformylation, hydrocyanation, cyclopropanation, C—C coupling,oligomerization and polymerization.
 17. A method comprising: reacting atleast one olefin with an N-phenylpyrrolebisphosphine-metal complex asclaimed in claim 8, wherein said reacting is selected from the groupconsisting of hydrogenation, isomerization, carbonylation,carboxylation, hydroformylation, hydrocyanation, cyclopropanation, C—Ccoupling, oligomerization and polymerization.